US8343597B2 - Norbornene polymer comprising photoreactive functional group having halogen substituent group, process for preparing the same, and alignment layer using the same - Google Patents

Norbornene polymer comprising photoreactive functional group having halogen substituent group, process for preparing the same, and alignment layer using the same Download PDF

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US8343597B2
US8343597B2 US13/123,444 US201013123444A US8343597B2 US 8343597 B2 US8343597 B2 US 8343597B2 US 201013123444 A US201013123444 A US 201013123444A US 8343597 B2 US8343597 B2 US 8343597B2
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US20110213048A1 (en
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Dong-Woo Yoo
Sung-Ho Chun
Dai-Seung Choi
Young-Chul Won
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LG Chem Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation

Definitions

  • the present invention relates to a photoreactive norbornene polymer comprising a photoreactive norbornene monomer, a process for preparing the same, and an alignment layer using the same and, more specifically, to a photoreactive norbornene polymer comprising a photoreactive norbornene monomer which has excellent adhesion property and can make an improvement in an orientation and an orientation rate of liquid crystals, a process for preparing the same, and an alignment layer using the same.
  • LCDs liquid crystal displays
  • TFT-LCD thin film transistor-liquid crystal displays
  • liquid crystals In order to be utilized as an optic switch in TFT-LCDs, liquid crystals should be initially oriented in a certain direction on a TFT layer which is disposed in the innermost part of a display cell, and a liquid crystal alignment layer is used to this end.
  • a current method of orienting liquid crystals in LCD which is called as a “rubbing process,” comprises applying a thermal resistant polymer such as a polyimide on a transparent glass to form a polymer alignment layer and rubbing the alignment layer with a rapidly rotating roller wound with a rubbing cloth made of nylon or rayon to impart an orientation.
  • a thermal resistant polymer such as a polyimide
  • the rubbing process leaves mechanical scratches on a surface of a liquid crystal alignment agent or generates such a large amount of electrostatic charges that it can destruct a thin film transistor. Also, fine fibers derived from a rubbing cloth can cause a defect and are hampering an improvement in production yield.
  • a newly designed manner of orienting liquid crystals is a UV-induced (i.e., light-induced) alignment of liquid crystals (hereinafter, referred to as “photoalignment”).
  • Photoalignment refers to a mechanism for forming a photo-polymerizable liquid crystal alignment layer wherein pre-polarized UV rays induce a photoreaction in a photosensitivy group of a polymer, and via this process the main chains of the polymers are aligned in such a direction that liquid crystals are oriented.
  • photoalignment is the photoalignment through photopolymerization disclosed in Jpn. J. Appl. Phys., Vol. 31, 1992, 2155 by M. Schadt et al., U.S. Pat. No. 5,464,669 by Dae S. Kang et al., and Jpn. J. Appl. Phys., Vol. 34, 1995, L1000 by Yuriy Reznikov.
  • polycinnamate polymers such as poly(vinyl cinnamate) (PVCN) and poly(vinyl methoxycinnamate) (PVMC) were mainly used as a photoalignment polymer.
  • PVN poly(vinyl cinnamate)
  • PVMC poly(vinyl methoxycinnamate)
  • UV irradiation makes a double bond in cinnamate group go through a [2+2] cycloaddition reaction to form a cyclobutane and thereby generates anisotropy, which allows liquid crystal molecules to be aligned in one direction and leads to an orientation of liquid crystals.
  • Japanese Patent Laid-open Publication No. Hei11-181127 teaches a method of producing a polymer alignment layer and an alignment layer produced thereby in which main chains of polyacrylate or polymethacrylate has side chains including photoreactive groups such as cinnamate group.
  • the polymer main chain has a poor thermal stability so that it has a negative impact on the stability of the alignment layer.
  • Korean Patent Laid-open Publication No. 2002-006819 discloses a method of utilizing a photoalignment layer made of polymethacrylate polymers, but the disclosed polymer has drawbacks such as a low surface hardness and a poor adhesion property.
  • Such a problem can be dealt with by combining a polymer having a photoreactive group with binder monomers such as acrylates or epoxy and hardening the resulting coating.
  • binder monomers such as acrylates or epoxy
  • an alignment layer with a higher hardness can be prepared through a light-induced reaction.
  • this approach ultimately results in a lower concentration of photoreactive groups affecting the orientation of liquid crystals and thus can lead to deterioration of the orientation.
  • an objective of the present invention is to provide a polymer that can improve orientation capabilities of an alignment layer by altering a substituent group of a photoreactive functional group and thereby making a change in the composition of the photoalignment layer.
  • the present invention provides a photoreactive norbornene polymer including a norbornene monomer represented by Chemical Formula (1) as follows:
  • p is an integer from 0 to 4.
  • R 1 , R 2 , R 3 , and R 4 is a radical selected from the group consisting of a group represented by Chemical Formula (1a) and a group represented by Chemical Formula (1b); and the rest of them are the same or different from each other and are independently selected from the group consisting of hydrogen; a halogen; a linear or branched C1-C20 alkyl group which is unsubstituted or substituted with one or more substituent group selected from a halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl and siloxy; a linear or branched C2-C20 alkenyl group which is unsubstituted or
  • both of R 1 and R 2 or both of R 3 and R 4 can be linked to each other to form C1-C10 alkylidene group, or R 1 or R 2 can be linked to one of R 3 and R 4 to form a saturated or unsaturated C4-C12 aliphatic ring or C6-C24 aromatic ring; and
  • A is a direct bond, —O—, —S—, or —NH—;
  • B is selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C20 alkylene, carbonyl, carboxy, ester, a substituted or unsubstituted C6-C40 arylene, and a substituted or unsubstituted C6-C40 heteroarylene;
  • X is —O— or —S—
  • R 9 is selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C20 alkylene, a substituted or unsubstituted C2-C20 alkenylene, a substituted or unsubstituted C3-C12 cycloalkylene, a substituted or unsubstituted C6-C40 arylene, a substituted or unsubstituted C7-C15 arylalkylene, and a substituted or unsubstituted C2-C20 alkynylene; and
  • R 10 , R 11 , R 12 , R 13 , and R 14 is a halogen or a C1-C20 alkyl substituted with a halogen; and the rest of them are the same or different from each other and are independently selected from the group consisting of a substituted or unsubstituted C1-C20 alkyl, a substituted or unsubstituted C1-C20 alkoxy, a substituted or unsubstituted C6-C30 aryloxy, a substituted or unsubstituted C6-C40 aryl, C6-C40 heteroaryl including a heteroatom of Group 14, Group 15, or Group 16, and a substituted or unsubstituted C6-C40 alkoxyaryl.
  • the present invention provides a process for preparing a photoreactive norbornene polymer which comprises polymerizing a norbornene monomer represented by Chemical Formula (1) at a temperature of 10-200° C. in the presence of a catalyst composition including a procatalyst which contains a Group 10 transition metal and a cocatalyst.
  • the present invention provides an alignment layer comprising the photoreactive norbornene polymer.
  • the present invention provides an alignment film comprising the photoreactive norbornene polymer.
  • the photoreactive norbornene polymer of the present invention includes a halogen substituent group, it is more exposed to the surface than other additives when being utilized to prepare an alignment layer and thus can achieve a higher orientation rate, an improved orientation, and a better adhesion property.
  • FIG. 1 is a view showing a structure of an alignment layer according to the present invention.
  • FIG. 2 is a view illustrating a comparison of the photoreactive norbornene polymer according to an embodiment of the present invention with a conventional poly(vinyl cinnamate) in terms of a thermal stability.
  • FIG. 3 is a view illustrating the anisotropy and the reactivity investigated by using UV-visible spectrometer.
  • FIG. 4 is a view illustrating an ESCA result for an alignment layer in accordance with Experimental Example 3 of the present invention.
  • the photoreactive norbornene polymer according to the present invention is characterized by comprising a norbornene monomer represented by Chemical Formula (1) as above.
  • the photoreactive norbornene polymer according to the present invention is structurally so robust and has such a high Tg (>300° C.) that it is superior to any known photoreactive polymer using acrylate polymers in a thermal stability. (see FIG. 2 )
  • the photoreactive norbornene polymer according to the present invention includes a norbornene monomer containing a certain photoreactive functional group and thereby has a halogen substituent group inserted therein. As a result of this, it is possible to improve a photoreactivity by a UV irradiation and an adhesion property.
  • the photoreactive norbornene polymer of the present invention includes a norbornene monomer in which a photoreactive cinnamate group is covalently bonded with norbornene.
  • an alignment layer comprising the photoreactive norbornene polymer gives a “compositional gradient” in the alignment layer and thus it can improve capabilities to orient liquid crystals.
  • the term “compositional gradient” in the alignment layer refers to a phenomenon in which after a binder and an alignment layer polymer that forms the alignment layer are coated onto a substrate, the binder is present in large quantities nearer to the substrate while the alignment layer material is present in large quantities further from the substrate; or vice versa.
  • the photoreactive material with a halogen substituent group more strongly causes this compositional gradient phenomenon with respect to the substrate as compared to other substituent groups.
  • the compositional gradient depending on the substrate occurs more severely due to the uniquely low polarity.
  • the substrate has a high polarity, a repulsive power makes the binder exist more abundantly near the substrate and the photoreactive material exist more abundantly near the surface, i.e. where it meets with liquid crystals. The more the alignment material exists where it meets with liquid crystals, the better orientation of liquid crystals can be obtained.
  • the norbornene monomer represented by Chemical Formula (1) can be explained in more detail as follows.
  • the polar group in Chemical Formula (1) is —R 5 OR 6 , —OR 6 , —OC(O)OR 6 , —R 5 OC(O)OR 6 , —C(O)OR 6 , —R 5 C(O)OR 6 , —C(O)R 6 , —R 5 C(O)R 6 , —OC(O)R 6 , —R 5 OC(O)R 6 , —(R 5 O) m —OR 6 , —(OR 5 ) m —OR 6 , —C(O)—O—C(O)R 6 , —R 5 C(O)—O—C(O)R 6 , —SR 6 , —R 5 SR 6 , —SSR 6 , —R 5 SSR 6 , —S( ⁇ O)R 6 , —R 5 C( ⁇ S)R 6 —, —R 5 C( ⁇ S)R 6 —, —R 5 R
  • R 5 is the same or different from each other and is independently a linear or branched C1-C20 alkylene which is unsubstituted or substituted with one or more substituent group selected from a halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl and siloxy; a linear or branched C2-C20 alkenylene which is unsubstituted or substituted with one or more substituent group selected from a halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralky
  • R 6 , R 7 and R 8 are the same or different from each other and is independently hydrogen; a halogen; a linear or branched C1-C20 alkyl which is unsubstituted or substituted with one or more substituent group selected from a halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl and siloxy; a linear or branched C2-C20 alkenyl which is unsubstituted or substituted with one or more substituent group selected from a halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl
  • n is independently an integer from 1 to 10.
  • the halogen in Chemical Formulae (1a) and (1b) comprises F, Cl, Br and I, and is more preferably F, but it is not limited thereto.
  • R 1 in Chemical Formula (1) is represented by Chemical Formula (1a) and at least one of R 10 , R 11 , R 12 , R 13 , and R 14 is F or C1-C20 alkyl substituted with F.
  • the photoreactive norbornene polymer of the present invention can include a repeating unit represented by Chemical Formula (2) as follows:
  • n 50 to 5,000 and p, R 1 , R 2 , R 3 , and R 4 are the same as defined above.
  • alkyl refers to a straight or branched chain, monovalent, saturated hydrocarbon with 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the alkyl group can be substituted with one or more halogen.
  • examples of the alkyl group include methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, iodomethyl, bromomethyl, and the like.
  • alkenyl refers to a straight or branched chain, monovalent hydrocarbon including at least one C—C double bond with 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms.
  • the alkenyl group can be bonded through a carbon atom including a C—C double bond or a saturated carbon atom.
  • the alkenyl group can be substituted with one or more halogen. Examples of the alkenyl group include ethenyl, 1-prophenyl, 2-prophenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl, dodecenyl, and the like.
  • cycloalkyl refers to a saturated or unsaturated, non-aromatic, monovalent, mono-, bi-, or tricyclic hydrocarbon with 3 to 12 cyclic carbons.
  • the cycloalkyl group can be substituted with one or more halogen.
  • examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphtalenyl, adamantly, norbonyl (i.e. bicyclo[2.2.1]hept-5-enyl), and the like.
  • aryl refers to a monovalent, mono-, bi-, or tricyclic, aromatic hydrocarbon with 6 to 20 cyclic atoms and preferably 6 to 12 cyclic atoms.
  • the aryl group can be substituted with one or more halogen. Examples of the aryl group include phenyl, naphthalenyl, fluorenyl, and the like.
  • alkoxyaryl refers to a group in which one or more hydrogen atom in the aryl as defined above is substituted with an alkoxy group.
  • alkoxyaryl group include methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentoxyphenyl, hexoxyphenyl, heptoxyphenyl, octoxyphenyl, nanoxyphenyl, methoxybiphenyl, ethoxybiphenyl, propoxybiphenyl, methoxynaphthalenyl, ethoxynaphthalenyl, propoxynaphthalenyl, methoxyanthracenyl, ethoxyantracenyl, propoxyanthracenyl, methoxyfluorenyl, and the like.
  • aralkyl refers to a group in which at least one hydrogen atom in the alkyl group as defined above is substituted with an aryl group.
  • the aralkyl group can be substituted with one or more halogen. Examples of the aralkyl group include benzyl, benzhydryl, trityl, and the like.
  • alkynyl refers to a straight or branched chain, monovalent hydrocharbon including at least one C—C triple bond with 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms.
  • the alkynyl group can be bonded through a carbon atom including a C—C triple bond or a saturated carbon atom.
  • the alkynyl group can be substituted with one or more halogen. Examples of the alkynyl group include ethynyl, propynyl, and the like.
  • alkylene refers to a straight or branched chain, bivalent, saturated hydrocarbon with 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the alkylene group can be substituted with one or more halogen. Examples of the alkylene group include methylene, ethylene, propylene, butylene, hexylene, and the like.
  • alkenylene refers to a straight or branched chain, bivalent hydrocarbon including at least one C—C double bond with 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms.
  • the alkenylene group can be bonded through a carbon atom including a C—C double bond and/or a saturated carbon atom.
  • the alkenylene group can be substituted with one or more halogen.
  • cycloalkylene refers to a saturated or unsaturated, non-aromatic, bivalent, mono-, bi-, or tricyclic hydrocarbon with 3 to 12 cyclic carbons.
  • the cycloalkylene group can be substituted with one or more halogen.
  • examples of the cycloalkylene include cyclopropylene, cyclobutylene, and the like.
  • arylene refers to a bivalent, mono-, bi-, or tricyclic, aromatic hydrocarbon with 6 to 20 cyclic atoms and preferably 6 to 12 cyclic atoms.
  • the arylene group can be substituted with one or more halogen.
  • the aromatic portion of the arylene group includes carbon atoms only. Examples of the arylene group include phenylene and the like.
  • arylalkylene refers to a bivalent part in which at least one hydrogen atom of the alkylene group as defined above is substituted with an aryl group, and it can be substituted with one or more halogen.
  • Examples of the arylalkylene group include benzylene and the like.
  • alkynylene refers to a straight or branched chain, bivalent hydrocarbon including at least one C—C triple bond with 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms.
  • the alkynylene group may be bonded through a carbon atom including a C—C triple bond or a saturated carbon atom.
  • the alkynylene group can be substituted with one or more halogen. Examples of the alkynylene group include ethynylene, propynylene, and the like.
  • the weight average molecular weight of the photoreactive norbornene polymer according to the present invention is preferably 10,000 to 1,000,000 but it is not limited thereto.
  • the photoreactive norbornene polymer of the present invention can be prepared by polymerizing the norbornene monomoer represented by Chemical Formula (1) at a temperature of 10-200° C. in the presence of a catalyst composition including a procatalyst containing a Group 10 transition metal and a cocatalyst.
  • reaction temperature lower than 10° C. is undesirable since it can lead to a significant decrease in the polymerization activity.
  • a reaction temperature higher than 200° C. is also undesirable since it can cause decomposition of the catalyst.
  • the procatalyst containing a Group 10 transition metal in the process for preparing the photoreactive norbornene polymer according to the present invention, one can use a compound with a Lewis base functional group which can readily take part in a Lewis acid-base reaction to separate out from a center transition metal in order that the procatalyst can be easily divided by the cocatalyst providing a Lewis acid so that the center transition metal is transformed into a catalyst active species.
  • procatalyst examples include Allylpalladium chloride dimer ([(Allyl)Pd(Cl)] 2 ), Palladium(II)acetate ((CH 3 CO 2 ) 2 Pd), Palladium(II)acetylacetonate ([CH 3 COCH ⁇ C(O ⁇ )CH 3 ] 2 Pd), NiBr(NP(CH 3 ) 3 ) 4 , [PdCl(NB)O(CH 3 )] 2 , and the like.
  • the cocatalyst can be at least one selected from the group consisting of: a first cocatalyst which provides a Lewis base capable of forming a weak coordinate bond with the metal of the procatalyst; and a second cocatalyst which provides a compound comprising a neutral Group 15 electron donor ligand.
  • the first cocatalyst providing a Lewis base that can form a weak coordinate bond with the metal in the procatalyst one can use a compound easily reacting with a Lewis base to make a vacant site in a transition metal and also forming a weak coordinate bond with a transition metal compound to stabilize the generated transition metal, or a compound providing such a compound.
  • Examples for the first cocatalyst include boranes such as B(C 6 F 5 ) 3 , borates such as dimethylanilinium tetrakis(pentafluorophenyl) borate, alkyl aluminums such as methylaluminoxane (MAO) or Al(C 2 H 5 ) 3 , and transition metal halides such as AgSbF 6 .
  • boranes such as B(C 6 F 5 ) 3
  • borates such as dimethylanilinium tetrakis(pentafluorophenyl) borate
  • alkyl aluminums such as methylaluminoxane (MAO) or Al(C 2 H 5 ) 3
  • transition metal halides such as AgSbF 6 .
  • Examples for the second cocatalyst providing a compound that includes a neutral Group 15 electron donor ligand include alkyl phosphine, cycloalkyl phosphine, phenyl phosphine, and the like.
  • the catalyst composition comprises 1 to 1,000 mole of the first cocatalyst and 1 to 1,000 mole of the second cocatalyst with respect to 1 mole of the procatalyst. If the content of the first and the second cocatalyst is less than 1 mole, the catalyst activation may not occur. If the content of the first and the second cocatalyst is more than 1,000 moles, the level of the catalyst activation can be lowered.
  • first cocatalyst and the second cocatalyst into one salt and use it to activate the catalyst.
  • a compound prepared by combining an alkyl phosphine with a borane to form an ionic bond therebetween can be used.
  • the present invention provides an alignment layer comprising the photoreactive norbornene polymer.
  • the present invention provides an alignment film comprising the photoreactive norbornene polymer.
  • the alignment layer and the alignment film can be manufactured by using any components and methods known in the art, except for comprising the photoreactive norbornene polymer of the present invention.
  • the alignment layer and the alignment film can be prepared by mixing the photoreactive norbornene polymer with a binder resin and a photoinitiator, dissolving them in an organic solvent, and then coating it onto a substrate and UV-curing it.
  • Acrylates can be used as the binder resin, and more specifically, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, tris(2-acrylolyloxyethyl) isocyanurate can be exemplified.
  • Examples for the photoinitiator includes Irgacure 907, Irgacure 819, and the like.
  • organic solvent examples include toluene, anisole, chlorobenzene, dichloroethane, cyclohexane, cyclopentane, propylene glycol methyl ether acetate, and the like.
  • the solid content of the solution properly ranges from 1 to 15%, and is preferably from 10 to 15% for casting it as a film and from 1 to 5% for preparing it as a thin film.
  • the substrate examples include a substrate comprising a cyclic polymer, a substrate comprising an acrylic polymer, a substrate comprising a cellulose polymer, and the like.
  • a coating method one can use a bar coating, spin coating, blade coating, and the like.
  • Example 2-3 Comparative Et PETA ⁇ ⁇ Exp.
  • Example 2-4 Comparative Et DPHA X ⁇ Exp.
  • Example 2-5 Comparative Et Isocyanurate X X Exp.
  • Example 2-6 Comparative PVCi PETA ⁇ ⁇ Exp.
  • Example 2-7 Comparative PVCi DPHA X ⁇ Exp.
  • Example 2-8 Comparative PVCi Isocyanurate X X Exp.
  • polymers substituted with fluorine gave a better result in the orientation and the adhesion property than polymers with other substituent groups. Due to a substance gradient occurring in a thin layer by fluorine, the alignment layer material is more abundant near the surface and the binder is more abundant near the substrate. This gives a superior orientation and an excellent adhesion to the substrate. Also, by comparison, PVCi is inferior to norbornene in the orientation and the adhesion property. Because PVCi fails to have such a thermal, structural stability as the norbornene has, it imparts little or no orientation and also shows a poor adhesion property as no gradient in the material concentration occurs.
  • a depth profile was determined with an ESCA for an alignment layer prepared by using the photoreactive norbornene polymer obtained from Example 3 in the same manner as described in Experimental Example 1.
  • a chemical species to be identified was fluorine, and the results are shown in FIG. 4 .
  • the amount of fluorine is higher on the surface, and it gradually decreases toward the substrate.
  • the capability of orienting liquid crystals depends on the concentration of the alignment material on the surface of the alignment layer.
  • concentration of the alignment material is so high that the orientation capability can be improved, but the hardness of the alignment layer would be deteriorated.
  • a binder such as acrylates, which in turn causes a decrease in the concentration of the alignment material and thus a deterioration of the orientation capability.
  • the alignment layers have a high anisotropy when they purely consist of the alignment material regardless of the substituent group. Also, from FIG. 3 , it can be understood that when the alignment material is mixed with a binder, the alignment layers have a similar anisotropy regardless of the substituent.

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US20110213048A1 (en) 2011-09-01
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